CN106823864B - A kind of preparation method of fluorescence mesoporous film - Google Patents
A kind of preparation method of fluorescence mesoporous film Download PDFInfo
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- CN106823864B CN106823864B CN201510881437.5A CN201510881437A CN106823864B CN 106823864 B CN106823864 B CN 106823864B CN 201510881437 A CN201510881437 A CN 201510881437A CN 106823864 B CN106823864 B CN 106823864B
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Abstract
A kind of preparation method of fluorescence mesoporous film, this method is that copolycondensation forms organic inorganic hybrid mesoporous film under template effect by the siloxanes containing cumarin functional group and positive compound of silicate class, using the dimerization and depolymerization regulation fluorescence intensity of cumarin at a particular wavelength, pass through the light-operated fluorescence mesoporous film for adjusting fluorescence intensity to be made.Fluorescence mesoporous film prepared by the present invention has the advantages that simple process, performance are stable, fluorescence intensity is adjustable.
Description
Technical field
The invention belongs to thin film materials arts, and in particular to a kind of preparation method of fluorescence mesoporous film.
Background technique
With the development of membrane technology, huge change is had occurred in people's lives.In protective coating, bio-matrix, gas
The fields such as separation, water body purification, optics, membrane technology play an important role.In optical field, film acts not only as coating
Protection is provided for optical device, a part that itself can also be used as optical device transmit to light or be swashed using incident light
It issues fluorescence and is used for specific occasion.
Currently, common film mainly has organic film, inoranic membrane and organic-inorganic hybrid films.Wherein, organic film is due to preparation
Simply, easy to form, it is widely used in industrial production, but it does not tolerate organic solvent, high temperature cracky, structural strength and pays no attention to
Think；Inoranic membrane structural strength is good, acid and alkali-resistance, organic solvent-resistant and can bear higher temperature, but its flexible poor, light transmittance
It is low；And organic-inorganic hybrid films combine the advantage of above-mentioned two classes film, have good plasticity, organic solvent-resistant, stable structure etc.
Multiple advantage.Due to its many physical and chemical performance, organic-inorganic hybrid films have become a kind of new material and are widely studied.
In organic-inorganic hybrid films, inorganic raw material is mainly silicon base compound, and preparation process is more mature, passes through colloidal sol
Gel method can prepare uniform gel, can be plated on different substrates surface by czochralski method, spin-coating method or vacuum sputtering
Film.And it is entrained in Organic Ingredients therein and the performance of film is played a crucial role.However traditional fluorescent film is usually simple
Single ground is doped to fluorescent dye in inoranic membrane skeleton, forms the film of the only fluorescent chromophore with fixed amount, excitation light source
Its fluorescence intensity is also fixed therewith after fixation, is not adjustable fluorescence intensity.(see, for example non-patent literature 1)
By Organic Ingredients of the covalent bonding with photoresponse in film raw material, the optical property and stabilization of film can be enhanced
Property, thus the ability for making film have photoresponse, and the order mesoporous skeleton structure of mesoporous film can promote photoresponse Organic Ingredients
Reaction efficiency preferably adjusts adjusting of the quantity realization of fluorescent chromophore in mesoporous film to fluorescence intensity under the stimulation of light.
Non-patent literature 1:Bouzid Menaa etc., Solid State Sciences, volume 2008,10,1200-1208 pages
Summary of the invention
It is an object of the invention to overcome the shortcomings of the prior art, a kind of preparation method of fluorescence mesoporous film is provided.
This method is that copolycondensation forms organic nothing under template effect by the siloxanes containing cumarin functional group and common siloxanes
Machine hybridized film, using the dimerization and depolymerization regulation fluorescence intensity of cumarin at a particular wavelength, so that light-operated tune can be passed through by being made
Save the fluorescence mesoporous film of fluorescence intensity.
The present invention provides the preparation methods of above-mentioned fluorescence mesoporous film, it is characterised in that: this method comprises the following steps:
With one in one of siloxanes containing cumarin functional group or two kinds or more and positive compound of silicate class
Kind or two kinds the above are raw materials, in solvent by acid or base catalysis prehydrolysis, add surfactant, be made pre-polymerization liquid；
Above-mentioned pre-polymerization liquid is coated to stromal surface, fluorescence mesoporous film is made in solvent flashing.Preparing, the mesoporous membrane process volatilization of fluorescence is molten
Pass through the light-operated fluorescence intensity for adjusting product before agent or after solvent flashing.Light-operated adjustment process is, using 300-380nm
The light of (preferably 320nm) or 200-280nm (preferably 250nm) wavelength irradiates the pre-polymerization liquid for being coated to stromal surface or fluorescence is mesoporous
Film irradiates the fluorescence intensity of time adjustment product by light；Fluorescence mesoporous film is produced using the light irradiation of 300-380nm wavelength
When, time adjustment fluorescence intensity is irradiated by light, the fluorescence intensity of fluorescence mesoporous film reduces with the increase of light irradiation time；It adopts
When producing fluorescence mesoporous film with the light irradiation of 200-280nm wavelength, time adjustment fluorescence intensity, fluorescence mesoporous film are irradiated by light
Fluorescence intensity increase with the increase of light irradiation time.
Specific steps are as follows:
It (1) will be in one of siloxanes containing cumarin functional group or two kinds or more and positive compound of silicate class
One or two or more kinds dissolution in a solvent, in solvent, by acid or base catalysis prehydrolysis, 0-80 DEG C of catalyzing hydrolysis temperature,
Time 5 minutes or more, surfactant is added, stirs evenly until being completely dissolved, obtained pre-polymerization liquid；
(2) pre-polymerization liquid in above-mentioned steps (1) is uniformly coated to stromal surface by czochralski method, solvent flashing, being made can
Pass through the light-operated fluorescence mesoporous film for adjusting fluorescence intensity.
The siloxanes containing cumarin functional group, siloxanes its structural formula of preferably cumarin female ring 7 substitutions is such as
Under,
A represents O, N, S, CH in structural formula2One of Deng；B represents (CH2)n, n 0-18；C represents O, N, S, CH2Deng
One of；D represents (CH2)n, n 0-18；E represents O (CH2)n CH3, n 0-4；
Wherein, preferably A is O, and B is (CH2)3, C S, D are (CH2)3, E OCH2CH3, structural formula (is denoted as chemical combination as follows
Object 1)；
The positive compound of silicate class, usually tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four
One of butoxy silane etc. or two kinds or more, preferably one of tetraethoxysilane or tetramethoxy-silicane or two kinds with
On, wherein more preferable tetraethoxysilane.
The solvent is any one or two kinds or more in alicyclic, arene, ketone or alcohol compound, preferably
The cycloalkane of 6-8 carbon atom, the aromatic hydrocarbon of 6-9 carbon atom, the aliphatic ketone of 3-6 carbon atom or 1-6 carbon atom rouge
One of fat alcohol or two kinds or more；Wherein, more preferable ethyl alcohol.
The acid or alkali are one of acetic acid, hydrochloric acid, sulfuric acid, ammonium hydroxide, sodium hydroxide, potassium hydroxide, preferably hydrochloric acid；
The surfactant is one of ionic surfactant or triblock copolymer or two kinds or more, and preferably three block is total
One of polymers or two kinds or more, more preferable CTAC, CTAB, P123, F127, wherein most preferably F127.
The matrix arbitrary substrate smooth or smooth for surface, preferably quartz glass, silicon plate, ceramic wafer or sheet metal,
Wherein, preferred quartz glass.
The molar ratio range of the siloxanes containing cumarin functional group and positive compound of silicate class is 0.0001-
10000, preferably 0.0005-50, more excellent is 0.005-0.5；The molar ratio range of the solvent and positive compound of silicate class is
0.5-100, preferably 1-100, more excellent is 1-20；The final concentration range of the acid or alkali is 0.001-0.1M, preferably 0.001-
0.01, more excellent is 0.005-0.01.
The optical power density range 0.1-10w/cm of the light source for light-operated adjusting2, the exposure time range is
1s-12h。
After the fluorescence mesoporous film as made from the above method is irradiated by above-mentioned light, cumarin molecule can make corresponding sound
Dimerization and depolymerisation should occur, the ratio of the molecule by adjusting two states can reach the purpose for adjusting fluorescence intensity, and
The siloxanes amount containing cumarin functional group being initially added determines the range of the fluorescence intensity of light-operated adjusting.
Compared with the prior art, the invention has the following beneficial effects:
The present invention is a kind of preparation method of fluorescence mesoporous film, the fluorescence mesoporous film and conventional method that this method is prepared
The fluorescent film of preparation is compared, and has regular meso-hole structure, has saved raw material while guaranteeing excellent fluorescence property；
Fluorophor is integrated on film by way of covalent bonding, improves the stability of fluorescence, by the way that fluorescence raw material is added
The maximum fluorescence intensity of amount control film；And light-operated adjusting fluorescence intensity can be passed through under conditions of not changing light source；Additionally have
Have that preparation process is simple, performance is stable, convenient for the advantage of mass production.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure of fluorescence mesoporous film.
Fig. 2 is the fluorescence spectra of fluorescence mesoporous film under 320nm exciting light, and solid line represents in embodiment 1 initial strong glimmering
Light mesoporous film, dotted line are represented through the hypofluorescence mesoporous film after light-operated adjusting, and the longitudinal axis is fluorescence intensity, and horizontal axis is wavelength.
Specific embodiment
The following examples will be further described the present invention, but the present invention is not limited to the following embodiments.
Embodiment 1
1,5mmol compound 1 is dissolved in 80mL ethyl alcohol.
2,1mol tetraethoxysilane is added.
3,9mL 0.05M hydrochloric acid is added after stirring 30min, continues stirring 2 hours.
4, F127 5g is added, stirring to solid is completely dissolved.
5, film is coated to Quartz glass surfaces.
6, fluorescence mesoporous film is made in solvent flashing, and aperture is about 6nm.
It 7, is 1.6w/cm with optical power density2The ultraviolet light 15min that wavelength is about 320nm, the fluorescence of adjusting film are strong
Degree.As shown in Figure 2, film fluorescence intensity is initially relatively strong, is hyperfluorescence mesoporous film；After being irradiated by 320nm light, fluorescence intensity subtracts
It is weak, it is changed into hypofluorescence mesoporous film.
Embodiment 2~8
On the basis of one operating condition of embodiment, change following condition and tested: dosage, the solvent kind of compound 1
Class, the wavelength of light and irradiation time.
Embodiment 2-8 difference from Example 1 see the table below:
The fluorescence mesoporous film in examples detailed above is tested respectively by fluorescence spectrum, the fluorescence intensity of fluorescence mesoporous film
Increase with the increase of compound 1, the maximum fluorescence intensity of film is determined with this.The fluorescence intensity of fluorescence mesoporous film is with 320nm
The increase of light irradiation time and reduce；After being irradiated again by 250nm light, fluorescence intensity increases with the increase of irradiation time.
The common mesoporous silicon fiml that fluorescence mesoporous film made from the above method is synthesized with conventional method is compared, the fluorescence
Mesoporous film structural strength is higher, it is not easy to crack, and have stable fluorescence；It, should compared with the fluorescent film of conventional dyes doping
More evenly, solvent resistant rinses the fluorescence of fluorescence mesoporous film, and has meso-hole structure, and luminous efficiency is higher, saves raw material, and energy
By the fluorescence intensity for switching the quantity adjusting film of the fluorescent chromophore of the wavelength regulation film of irradiation light.
Claims (22)
1. a kind of preparation method of fluorescence mesoporous film, it is characterised in that: with one of the siloxanes containing cumarin functional group
Or the above are raw materials for one of two kinds or more and positive compound of silicate class or two kinds, it is pre- by acid or base catalysis in solvent
Hydrolysis, adds surfactant, and pre-polymerization liquid is made；Above-mentioned pre-polymerization liquid is coated to stromal surface, fluorescence is made in solvent flashing
Mesoporous film.
2. preparation method described in accordance with the claim 1, it is characterised in that:
Pass through the light-operated fluorescence intensity for adjusting product before preparing the mesoporous membrane process solvent flashing of fluorescence or after solvent flashing；
Light-operated adjustment process is that the pre-polymerization liquid of stromal surface is coated to using the light irradiation of 300-380nm or 200-280nm wavelength
Or fluorescence mesoporous film, the fluorescence intensity of time adjustment product is irradiated by light；
When producing fluorescence mesoporous film using the light irradiation of 300-380nm wavelength, time adjustment fluorescence intensity, fluorescence are irradiated by light
The fluorescence intensity of mesoporous film reduces with the increase of light irradiation time；
When producing fluorescence mesoporous film using the light irradiation of 200-280nm wavelength, time adjustment fluorescence intensity, fluorescence are irradiated by light
The fluorescence intensity of mesoporous film increases with the increase of light irradiation time.
3. preparation method according to claim 2, it is characterised in that: light-operated adjustment process is, using 320nm or 250nm
The light irradiation of wavelength is coated to the pre-polymerization liquid or fluorescence mesoporous film of stromal surface, and the fluorescence for irradiating time adjustment product by light is strong
Degree.
4. preparation method described in accordance with the claim 1, it is characterised in that: specific steps are as follows:
(1) by one of siloxanes containing cumarin functional group or two kinds or more and one of positive compound of silicate class
Or two kinds or more dissolve in a solvent, in solvent, passes through acid or base catalysis prehydrolysis, 0-80 DEG C of catalyzing hydrolysis temperature, time 5
Minute or more, surfactant is added, stirs evenly until being completely dissolved, obtained pre-polymerization liquid；
(2) pre-polymerization liquid in above-mentioned steps (1) is uniformly coated to stromal surface by czochralski method, solvent flashing, being made can pass through
The light-operated fluorescence mesoporous film for adjusting fluorescence intensity.
5. according to preparation method described in claim 1 or 4, it is characterised in that:
The siloxanes containing cumarin functional group is that siloxanes its structural formula of cumarin female ring 7 substitutions is as follows,
A represents O, N, S, CH in structural formula2One of Deng；B represents (CH2)n, n 0-18；C represents O, N, S, CH2One in
Kind；D represents (CH2)n, n 0-18；E represents O (CH2)n CH3, n 0-4.
6. preparation method according to claim 5, it is characterised in that:
A is O, and B is (CH2)3, C S, D are (CH2)3, E OCH2CH3, structural formula is as follows (being denoted as compound 1)；
7. according to preparation method described in claim 1 or 4, it is characterised in that:
The positive compound of silicate class is tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four butoxy silicon
One of alkane etc. or two kinds or more.
8. preparation method according to claim 7, it is characterised in that: the positive compound of silicate class is tetraethoxy-silicane
One of alkane or tetramethoxy-silicane or two kinds.
9. preparation method according to claim 7, it is characterised in that: the positive compound of silicate class is tetraethoxy-silicane
Alkane.
10. according to preparation method described in claim 1 or 4, it is characterised in that:
The solvent is any one or two kinds or more in alicyclic, arene, ketone or alcohol compound.
11. preparation method according to claim 10, it is characterised in that: the solvent be 6-8 carbon atom cycloalkane,
One of fatty alcohol of the aromatic hydrocarbon of 6-9 carbon atom, the aliphatic ketone of 3-6 carbon atom or 1-6 carbon atom or two kinds with
On.
12. preparation method according to claim 10, it is characterised in that: the solvent is ethyl alcohol.
13. according to preparation method described in claim 1 or 4, it is characterised in that:
The acid or alkali are one of acetic acid, hydrochloric acid, sulfuric acid, ammonium hydroxide, sodium hydroxide, potassium hydroxide.
14. preparation method according to claim 13, it is characterised in that: the acid is hydrochloric acid.
15. according to preparation method described in claim 1 or 4, it is characterised in that:
The surfactant is one of ionic surfactant or triblock copolymer or two kinds or more.
16. preparation method according to claim 15, it is characterised in that: the surfactant is in triblock copolymer
One or two or more kinds.
17. preparation method according to claim 15, it is characterised in that: the surfactant be CTAC, CTAB,
P123、F127。
18. preparation method according to claim 15, it is characterised in that: the surfactant is F127.
19. according to preparation method described in claim 1 or 4, it is characterised in that:
The molar ratio range of the siloxanes containing cumarin functional group and positive compound of silicate class is 0.0001-10000；
The molar ratio range of the solvent and positive compound of silicate class is 0.5-100；
The final concentration range of the acid or alkali is 0.001-0.1M.
20. preparation method according to claim 19, it is characterised in that: the siloxanes containing cumarin functional group with
The molar ratio range of positive compound of silicate class is 0.0005-50；
The molar ratio range of the solvent and positive compound of silicate class is 1-100；
The final concentration range of the acid or alkali is 0.001-0.01M.
21. preparation method according to claim 19, it is characterised in that: the siloxanes containing cumarin functional group with
The molar ratio range of positive compound of silicate class is 0.005-0.5；
The molar ratio range of the solvent and positive compound of silicate class is 1-20；
The final concentration range of the acid or alkali is 0.005-0.01M.
22. preparation method according to claim 2, it is characterised in that: the optical power density range for light-operated adjusting
0.1-10w/cm2, the exposure time range is 1s-12h.
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